3133-27-5Relevant academic research and scientific papers
Chemoselective reduction of the phosphoryl bond of O-alkyl phosphinates and related compounds: An apparently impossible transformation
Kenny, Niall P.,Rajendran, Kamalraj V.,Gilheany, Declan G.
, p. 16561 - 16564 (2015/11/18)
A method is reported for the phosphoryl bond cleavage of O-alkyl phosphinates, phosphinothioates and certain phosphonamidates to furnish the corresponding P(iii) borane adducts. The two-step procedure relies upon initial activation of the phosphoryl bond with an alkyl triflate, followed by reduction of the resulting intermediate using lithium borohydride.
Alkali metal ion catalysis and inhibition in nucleophilic substitution reactions of 3,4-Dinitrophenyl diphenylphosphinothioate with alkali metal ethoxides in anhydrous ethanol: Effect of changing electrophilic center from P=O to P=S
An, Jun-Sung,Namkoong, Gil,Kang, Ji-Sun,Um, Ik-Hwan
, p. 2423 - 2427 (2012/06/01)
Pseudo-first-order rate constants (kobsd) have been measured spectrophotometrically for nucleophilic substitution reactions of 3,4-dinitrophenyl diphenylphosphinothioate 9 with alkali metal ethoxides (EtOM, M = Li, Na, K) in anhydrous ethanol a
Reactivity of X3P compounds with elemental sulfur, carbon disulfide or both, to yield X3PS, X3RCS2 or X3P.Sn.CS2 adducts
Demarcq, Michel C.
, p. 307 - 320 (2007/10/03)
Kinetic constants k2 have been obtained for the reaction of sulfur with 25 PIII compounds in toluene or hexane. In the series PhnMe3-nP (n = 1-3) or PhnBu3-nP (n = 0-3), log k2 decreases linearly with Σχi (χi=Tolman's electronic parameter of each ligand on P), taken as a gauge for the donor strength of P. Dramatic deviations from additivity are observed for the series PhnP(OEt)3-n, PhnP(OEt)3-n, and BunP(OEt)3-n(n = 0-3); the deviation is smaller for PhnPCl3-n, and even smaller for PhnP(NEt2)3-n . The results are discussed in terms of P-coordination (PIV vs. PV), stability and geometry of the intermediate X3P.S8 or of the transition state leading to this adduct, emphasis being laid on the donor/acceptor character of the P site. A similar dependence on X governs the reactivity of X3P with S8, CS2 or both, to give X3PS, X3P.CS2 (binary red adduct) or X3P.Sn.CS2 (ternary yellow adduct) respectively; an explanation for this parallelism is proposed.
α-SUBSTITUIERTE PHOSPHONATE. 70. UNTERSUCHUNGEN UEBER METHYLTHIOMETHANBISPHOSPHORYLDERIVATE
Costisella, Burkhard,Ozegowski, Sigrid,Gross, Hans
, p. 169 - 176 (2007/10/02)
Thiophilic reaction of ethyl diphenylphosphinite with phosphonodithioformate 1 gave the ylid 9, which could be transformed with HCl to the bisphosphorylcompound 10.Chlorine reacted with 9 to the chlorinated bisphosphorylderivative 12b, with the ylid 2 analogously 12a was formed.With BTMS/H2O 10 could be dealkylated to the acid 11b, the bisphosphonate 3 in similar way to 11a.Using the Horner-method 3 was transformed to the methylthiovinylphosphonates 17, which could be converted to the acids 18 using the BTMS/H2O-method.Key-words: Methylthiomethane-bisphosphonic acid; alkoxyphosphoniumylid; Horner-reaction; methylthiovinylphosphonate.
Kinetics and mechanism of the reaction of trico-ordinate phosphorus ompounds with octasulphur
Lloyd, John R.,Lowther, Nicholas,Zsabo, G.,Hall, C. Dennis
, p. 1813 - 1818 (2007/10/02)
Kinetic data and activation parameters are reported for the reactions of a series of phosphites, arylphosphonites, diarylphosphinites, and triarylphosphines with octasulphur (S8) in toluene as solvent.For the phosphites the data are explained in terms of changes in p-character of the Ione-pair orbital on phosphorus and inductive electron donation by the alkyl groups.The rates of reaction of series of arylphosphonites, diarylphosphonites, and triarylphosphones correlate with the Hammett ? constants to give ? values of -3.0, -3.0, and -2.5, respactively, and the results are discussed in terms of the Reactivity-Selectivity Principle and the biphilic mechanism or insertion of trico-ordinate phosphorus into ?-bonds.
